Unique supported metallocene catalyst for producing syndiotactic styrenic polymer

ABSTRACT

The present invention provides a supported catalyst comprising (A) a polymer (B) a supporter, (C) a transition metal compound, and optionally (D) (a) a compound which can form an ionic complex by the reaction with the transition metal compound or (b) a specific oxygen-containing compound, and (E) an alkylaluminum compound. The supported catalyst according to present invention, which has a high activity, can be used for preparing a styrenic polymer with a high syndiotacticity. The supported catalyst can be used in combination with a cocatalyst, preferably an alcyl aluminoxane.

FIELD OF THE INVENTION

[0001] The present invention relates to a supported catalyst forpreparing a syndiotactic styrenic polymer. More particularly, thepresent invention relates to a supported catalyst having high activityfor preparing a styrenic polymer with a high syndiotacticity and a highcrystallinity.

BACKGROUND OF THE INVENTION

[0002] Syndiotactic polystyrene (sPS) was first synthesized in 1986(Ishihara et al., Macromolecules 1986, 19, 2464), using the homogeneousorganometallic catalytic system based on a titanium compound andmethylaluminoxane (MAO). Syndiotactic polystyrene is a very attractivepolymer. The polymer shows a low specific gravity, a low dielectricconstant, a high modulus of elasticity and an excellent resistance tochemicals. Accordingly the syndiotactic polystyrene has become apromising material for various applications in the automotive,electronic and packaging industries.

[0003] However, the commercialization of a syndiotactic polystyrene hassome serious problems, i.e. serious reactor fouling or lump, and lowflowability of the product powder resulted from its unsatisfactorymorphology. The problems are remained unsolvable if only using ahomogeneous catalyst. These problems are solved by using a catalystsupported to an organic or inorganic support instead of using a generalhomogeneous catalyst on polymerization. However, the activity of asupported catalyst is generally much lower than that of thecorresponding homogeneous catalyst by the order of magnitude of 2-3, andthe polymerization activity of a syndiotactic polystyrene is, generally,much lower than that of polyolefin. Therefore it is very difficult toprepare a supported catalyst having acceptable activity for producing asyndiotactic polystyrene.

[0004] So far, four basic methods have been developed for metallocenecatalyst systems for production of polyolefin as follow:

[0005] 1. direct adsorption of metallocene into the support surfaceinvolving physisorption or chemisorption of metallocene (directheterogenization);

[0006] 2. initial adsorption of methylaluminoxane (MAO) into thesupport, followed by adsorption of metallocene (indirectheterogenization);

[0007] 3. covalent bonding of metallocene to a carrier by a ligand,followed by activation with MAO; and

[0008] 4. use of an organic compound which is able to react with thehydroxyl group of an inorganic support surface such as silica and toform a complex with metallocene to be supported, which is represented bythe following reaction as one example:

Si—OH+HO—R—OH→Si—O—R—OH→Si—R—O . . . Metallocene

[0009]  where R is a hydrocarbon compound.

[0010] Either the direct loading of a metallocene catalyst on a support(Method 1) or the indirect loading on a MAO treated support (Method 2,Kaminsky et al., J. Polym. Sci.: Part A: Polym. Chem. 1999, 37, 2959)does not provide a good activity for styrenic polymerization. Method 3relates to a complex chemistry and difficulties arise when bonding themetallocene to the support surface. A spacer between support andmetallocene was introduced in Method 4, but the results, as reported bySpitz et al. (Macromol. Chem. Phys. 1999, 200, 1453), show that there isno any enhancement of styrene polymerization activity.

[0011] Until now, very few reports can be seen in the area of supportedcatalyst for producing syndiotactic polystyrene. Silica (Kaminsky etal., J. Polym. Sci.: Part A: Polym. Chem. 1999, 37, 2959), alumina(Spitz et al., Macromol. Chem. Phys. 1999, 200, 1453) and polymer (Yu etal., J. Polym. Sci.: Part A: Polym. Chem. 1996, 34, 2237) have been usedas a support for preparation of a supported catalyst for producingsyndiotactic polystyrene. Unfortunately, all these supported catalystsare not applicable because of extremely low activity. Therefore, asupported catalyst with high activity for producing syndiotacticstyrenic polymer is highly expected.

[0012] Accordingly, the present inventors have developed a supportedmetallocene catalyst with a high activity in combination with acocatalyst for preparing a styrenic polymer with a high syndiotacticity.

SUMMARY OF THE INVENTION

[0013] The present invention provides a supported catalyst comprising(A) a polymer, (B) a supporter, (C) a transition metal compound, andoptionally (D) (a) a compound which can form an ionic complex by thereaction with the transition metal compound or (b) a specificoxygen-containing compound, and (E) an alkylaluminum compound. Thesupported catalyst can be used in combination with a cocatalyst,preferably an alkyl aluminoxane.

[0014] A feature of the present invention is to provide a supportedcatalyst with a high activity for preparing a styrenic polymer having ahigh syndiotacticity.

[0015] Another feature of the present invention is to provide asupported catalyst for preparing a styrenic polymer, which cansignificantly diminish reactor fouling or lump on polymerization, andprepare a polymer having a good flowability and a high crystallinity.

[0016] Other features and advantages of this invention will be apparentfrom the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWING

[0017]FIG. 1 is a schematic diagram of a process for preparing asupported catalyst according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0018] Catalyst System

[0019] The present invention provides a supported catalyst comprising(A) a polymer, (B) a support, (C) a transition metal compound, andoptionally (D) (a) a compound which can form an ionic complex by thereaction with the transition metal compound or (b) a specificoxygen-containing compound, and (E) an alkylaluminum compound. Thedetailed description of each component of a catalyst system is asfollows.

[0020] (A) Polymer

[0021] It is believed that the key point to obtain a high activitymetallocene supported catalyst is to insulate the metallocene catalystto be supported from the poisonous surface of the support, mostlysilica, without deterioration of the advantages of the supportedcatalyst.

[0022] For instance, when a homogeneous catalyst reacts with aninorganic support, the catalyst can be apt to react with hydroxyl groupsor Si—OH groups in case of silica on the surface of a support. However,the method is not effective because, even though the hydroxyl groups ofthe support are capped, the non-hydroxyl group area of the surface ofthe support (—Si—O—Si—, in case of silica) still remains bare. The bareacidic surface is poisonous to the catalyst, so results in rapiddeclination of the catalytic activity. Therefore, this method has beenreported not to be effective.

[0023] With this thought in mind, the present inventors have used apolymer to completely insulate the homogeneous catalyst to be supportedfrom the poisonous surface, i.e. oxygen atom (—Si—O—Si—) of the support,thereby functioning an insulation layer between the catalyst and thesupport. Thus, the polymer of the present invention should be harmlessto catalytic performances, have chemical or physical interaction withthe catalyst and support, and be insoluble in the styrenic monomer orpolymerization solvent after loading a catalyst.

[0024] The polymers to meet the requirements described above are organicpolymers containing particular polar groups. The particular polar groupsof the polymer interact chemically or physically with the surface of asupport. Accordingly the polymer can be completely absorbed on thesurface of the support to form an insulation film, somewhat like acoating process. And the polar groups absorb a metallocene catalyst tobe supported by formation of a stable complex. Therefore the coatingfilm acts an insulator for support on loading a homogeneous catalyst.

[0025] Representative polymers suitable for this purpose includeacrylonitrile-containing polymers and copolymers, hydroxylgroup-containing polymer and copolymers, acrylic and acrylate polymersand copolymers, maleic anhydride-containing copolymers and maleicanhydride modified polymers, acetate containing polymers and copolymers,polyethers, polyketones, and polyamide polymer and copolymer.

[0026] Specific examples of the acrylonitrile-containing polymers andcopolymers are polyacrylonitrile, poly(acrylonitrile-block-styrene),poly(styrene-co-acrylonitrile), acrylonitrile-butadiene-styrene resin,poly(acrylonitrile-co-butadiene), poly(acrylonitrile-co-isoprene), etc.The acrylonitrile content in the copolymers is not specifically limited,but is usually about from 0.1 to 100% by weight, preferably about from 2to 50% by weight. And the degree of the poly(styrene-co-acrylonitrile)is preferably at least about 5.

[0027] The amount of polymer for the insulation layer is not limited,but is preferably in the range of about 0.0001 to 99.999% by weight asper the supported catalyst.

[0028] (B) Support

[0029] A support used for preparation of the supported catalystaccording to the present invention includes both inorganic supports andorganic supports.

[0030] The representative examples of the inorganic supports includesilica gel, alumina, silica-alumina gel, zeolite, mica powder, clays,molecular sieves, metal oxide compounds, metal halogenides, metalcarbonates and metal powder. Silica gel, silica-alumina gel and aluminaare most preferable among the inorganic solids. An organic solid mayinclude poly(styrene-co-divinylbenzene) beads, and starch powder, etc.

[0031] The amount of support is not limited, but is preferably in therange of about 0.0001 to 99.999% by weight as per the supportedcatalyst.

[0032] The transition metal compound used as a homogeneous catalyst inthe present invention is a Group IVB metal compound represented by thefollowing formula (A) or (B):

MR¹ _(a)R² _(b)R³ _(c)X_(4−(a+b+c))  (I)

MR¹ _(d)R² _(e)X_(3−(d+e))  (II)

[0033] where M is an atom of Group IVB, R¹, R² and R³ are independentlya hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbonatoms, an alkylaryl group having 6 to 20 carbon atoms, an arylalkylgroup having 6 to 20 carbon atoms, an aryloxy group having 1 to 20carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienylgroup or an indenyl group, X is a halogen atom, a, b and c are aninteger of 0 to 4, and d and e are an integer of 0 to 3.

[0034] Representative examples of the alkyl group having 1 to 20 carbonatoms as represented by R¹, R² or R³ are a methyl, an ethyl, a propyl, abutyl, an amyl, an isoamyl, an isobutyl, an octyl and a 2-ethylhexyl.

[0035] Representative examples of the alkoxy group having 1 to 20 carbonatoms are a methoxy, an ethoxy, a propoxy, a butoxy, an amyloxy, ahexyloxy and a 2-ethylhexyloxy.

[0036] Representative example of the aryl, alkylaryl or arylalkyl having6 to 20 carbon atoms are a phenyl, a tolyl, a xylyl and a benzy group.

[0037] In the general formulae (I) and (II), R¹, R² and R³ may be thesame or different one another.

[0038] The transition metal component (C) used for preparation of thesupported catalyst according to the present invention further includes,besides single nuclear catalysts as represented in formulae (I) or (II),binuclear and multiple-nuclear catalysts as well.

[0039] The binuclear catalyst is represented by the following formula(III), (IV) or (V):

[0040] where M¹ and M² is independently a IVB group atom of the PeriodicTable; R⁴, R⁵, and R⁶ are independently an alkyl group having 1 to 20carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylarylgroup having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20carbon, a cyclopentadienyl group, a substituted cyclopentadienyl groupor an indenyl group; and f is independently an integer of 0 to 2.

[0041] Examples of the alkyl group having 1 to 20 carbon atoms asrepresented by R⁴, R⁵, and R⁶ include a methyl, an ethyl, a propyl, abutyl, an amyl, an isoamyl, an isobutyl, an octyl, and a 2-ethylhexylgroup; and examples of the aryl, alkylaryl, or arylalkyl group having 6to 20 carbon atoms include a phenyl, a tolyl, a xylyl, and a benzylgroup. R⁴, R⁵, and R⁶ may be the same or different.

[0042] In the general formulae (III), (IV) and (V), R⁴, R⁵ and R⁶ may beidentical or different one another.

[0043] The multi-nuclear catalyst is represented by the formula (VI):

[0044] where R⁷ is an alkyl group having 1 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20carbon atoms, an arylalkyl group having 6 to 20 carbon, acyclopentadienyl group; the polymerization degree of the polymer is 5 to10000; and n is an integer of 0 to 1000.

[0045] The transition metal compound (C) may be used alone or incombination of two or more types. The amount of the transition metalcompound (C) is not limited, but is preferably in the range of about0.0001 to 30.0% by weight as per the supported catalyst.

[0046] (D) Compound, Which Can Form an Ionic Complex by the ReactionWith a Transition Metal Compound, or Oxygen-Containing Compound

[0047] In the preparation process of the supported catalyst of thepresent invention, (a) a compound, which can form an ionic complex bythe reaction with a transition metal compound, or (b) anoxygen-containing compound may be optionally used. The above component(a) is composed of an anion and a cation.

[0048] Specific examples of the anion include B(C₆F₅)₄ ⁻, B(C₆HF₄)₄ ⁻,B(C₆H₂F₃)₄ ⁻, B(C₆H₃F₂)₄ ⁻, B(C₆H₄F)₄ ⁻, B(C₆CF₃F₄)₄ ⁻, BF₄ ⁻, PF₆ ⁻,P(C₆F₅)₆ ⁻, and Al(C₆HF₄)₄ ⁻. Specific examples of the metal cationinclude Cp₂Fe⁺, (MeCp)₂Fe⁺, (tButCp)₂Fe⁺, (Me₂Cp)₂Fe⁺, (Me₃Cp)₂Fe⁺,(Me₄Cp)₂Fe⁺, (Me₅Cp)₂Fe⁺, Ag⁺, Na⁺, and Li⁺. Other examples of thecation include ions containing nitrogen such as a pyridinium ion,2,4-dinitro-N,N-diethylanilinium ion, diphenyl ammonium ion,p-nitroanilinium, 2,5-dichloroanilinium ion,p-nitro-N,N-dimethylanilinium ion, quinolinium ion,N,N-dimethylanilinium ion, and N,N-diethylanilinium ion; carbeniumcompounds such as triphenylcarbenium ion, tri(4-methylphenyl)carbeniumion, and tri(4-methoxyphenyl)carbenium ion; an alkylphosphonium ion suchas CH₃PH₃ ⁺, C₂H₅PH₃ ⁺, C₃H₇PH₃ ⁺, (CH₃)₂PH₂ ⁺, (C₂H₅)₂PH₂ ⁺, (C₃H₇)₂PH₂⁺, (CH₃)₃PH⁺, (C₂H₅)₃PH⁺, (C₃H₇)₃PH⁺, (CF₃)₃PH, (CH₃)₄P⁺, (C₂H₅)₄P⁺, and(C₃H₇)₄P⁺; and arylphosphonium ion such as C₆H₅PH₃ ⁺, (C₆H₅)₂PH₂ ⁺,(C₆H₅)₃PH⁺, (C₆H₅)₄P⁺, (C₂H₅)₂(C₆H₅)PH⁺, (CH₃)(C₆H₅)PH₂ ⁺,(CH₃)₂(C₆H₅)PH⁺ and (C₂H₅)₂(C₆H₅)₂PH⁺.

[0049] The compound (a), which can form an ionic complex by the reactionwith the transition metal compound of the component (C), is a boratecompound. The borate compound includes B(C₆F₅)₃, B(C₆HF₄)₃, B(C₆H₂F₃)₃,B(C₆H₃F₂)₃, B(C₆H₄F)₃, B(C₆CF₃F₄)₃, BF₃, PF₅, P(C₆F₅)₅, and Al(C₆HF₄)₃.

[0050] The oxygen-containing compound (b) may be an alkyl aluminoxanerepresented by the following formula, which is a product of the reactionof an alkylaluminum and a condensation reagent (e.g. water).

[0051] where R⁸ is an alkyl group having 1 to 8 carbon atoms, and j is ainteger of 2 to 50.

[0052] The chain structure of an alkyl aluminoxane may be a linear or acyclic structure.

[0053] (E) Alkylaluminum Compound

[0054] In the preparation process of the supported catalyst of thepresent invention, an alkylaluminum compound represented by thefollowing formula (H) can be optionally used:

AlR⁹ ₃  (H)

[0055] where R⁹ is an alkyl group having 1 to 8 carbon atoms.

[0056] Cocatalyst

[0057] The supported catalyst of the present invention is preferable touse in combination with a cocatalyst for preparing a syndiotacticpolymer. The component (D) individually or in combination with thecomponent (E) may be used as the cocatalyst.

[0058] Monomer

[0059] The styrenic monomer is polymerized to prepare syndiotacticstyrenic polymer by using the supported catalyst provided by the presentinvention. The styrenic monomer is represented by the formula (IX):

[0060] where each R¹⁰ is selected from a hydrogen atom, a halogen atom,or a substituent containing a carbon atom, an oxygen atom, a nitrogenatom, a sulfur atom, a phosphorous atom, or a silicon atom, and krepresents an integer of 1 to 3.

[0061] The styrenic monomer may be homopolymerized or two or more kindsof styrenic monomers may be copolymerized.

[0062] The monomers, which can be polymerized by the supported catalystaccording to the present invention, are not limited to the styrenicmonomers. Olefin monomers represented by the general formula (J) canalso be homopolymerized and copolymerized with other olefin monomers orstyrenic monomers.

[0063] where R¹¹ is selected from a hydrogen atom, and a linear orcyclic alkyl group having 1 to 20 carbon atoms.

[0064] Among the components for preparing a supported catalyst of thepresent invention, components (A), (B), and (C) are essentialcomponents, and components (D) and (E) as optional components may beused with components (A), (B), and (C).

[0065] The amount of components (A) and (B) in the supported catalyst isnot specially limited. But, the amount of component (A) is preferably atleast 0.001% by weight and that of component (B) is preferably at least70% by weight. The amount of component (C) is also not speciallylimited, but it is preferably about 0.001 to 30% by weight. Finally, theamount of components (D) and (E) is also not specially limited.

[0066]FIG. 1 is a schematic diagram of process for preparing a supportedcatalyst according to the present invention. The reaction procedures andthe addition sequences of these components for preparation of supportedcatalyst are not specifically limited, but those as shown in FIG. 1 arepreferred.

[0067] The solvent used for preparation of the supported catalyst is notspecifically limited, but aliphatic and aromatic hydrocarbon solventsare preferred, which is easily conducted by an ordinary skilled personin the art to which the present invention pertains. The reactiontemperature for preparation of the supported catalyst is usually aboutfrom −100° C. to 150° C., preferably from 20 to 70° C.

[0068] The invention may be better understood by reference to thefollowing examples, which are intended for the purpose of illustrationand are not to be construed as in any way limiting the scope of thepresent invention, which is defined in the claims appended hereto. Inthe following examples, all parts and percentage are by weight unlessotherwise indicated.

EXAMPLES Example 1 Preparation of Homogeneous Catalyst,Tri(4,4′-isopropylidenediphenol)di(pentamethylcyclopentadienyltitanium)[(CH₃)₅CpTi]₂[(CH₃)₂C(C₆H₄O)₂]

[0069] Preparation Method 1

[0070] To a dried 250 ml flask equipped with a magnetic stirrer, 80 mlof purified toluene, 2.3 g (10 mmol) of bisphenol-A and 5 ml (35.9 mmol)of dried triethyl amine (Aldrich, 99.5% of purity) were added under anatmosphere of nitrogen. The resultant solution was clear and colorless.The solution was cooled to −78° C. by an acetone-liquid nitrogen bath.With vigorous stirring, 2.0 g (6.8 mmol) of Cp*TiCl₃ dissolved in 70 mlof toluene was added dropwise by cannular. The reaction system, then wasslowly warmed to room temperature and kept for 4 hours. The color of thesolution was changed from red to yellow, and a white precipitate wasyielded. The precipitate was filtered, and the solution was evacuated todry. As a result, 3.4g of a yellow solid was obtained in a quantitativeyield.

[0071] Preparation Method 2

[0072] To a dried 250 ml flask equipped with a magnetic stirrer, 80 mlof purified toluene, and 2.42 g (10.6 mmol) of bisphenol-A were addedunder an atmosphere of nitrogen, and then 2.0 g (7.1 mmol) ofCp*Ti(OCH₃)₃ dissolved in 70 ml of toluene was added dropwise withstirring. The reaction system then was kept at room temperature for 4hours, and was dried under vacuum. As a result, 3.4 g of a yellow solidwas obtained in a quantitative yield.

[0073] By ¹H NMR and ¹³C NMR, the products obtained by the two methodsmentioned above, have exactly the same structure represented by thefollowing formula (XI). The homogeneous catalyst as made was namedHomoCat-1.

Example 2

[0074] To a dried 250 ml flask equipped with a magnetic stirrer, 4 g ofsilica (Aldrich, calcinated at 700° C.), 0.5 g of styrene-acrylonitrile(SAN, 23 wt % of acrylonitrile content, Mw: 90,000) polymer, and 80 mlof toluene were added under an atmosphere of nitrogen. The resultantslurry was stirred at a room temperature for 2 hours until completedissolution of SAN polymer. The toluene was then removed by decantationfollowed by drying under vacuum. Thus, a white solid support precursor,and 2 mmol of methylaluminoxane (MAO) in 80 ml of toluene was added atroom temperature. The slurry was kept at room temperature with stirringfor 30 minutes, and then toluene was removed by decantation followed bydrying under vacuum. As a result, a white solid was obtained as asupport precursor II. 0.2 mmol of a homogeneous catalyst, HomoCat-1prepared by Example 1, in 80 ml of toluene was injected by cannular tothe support precursor II. The resultant slurry was kept at roomtemperature with stirring for 30 minutes and then was filtered. Thesolid was washed with 50 ml of toluene for 3 times, and then was driedby vacuum.

[0075] The resultant toluene solution was analyzed by ICP, its contentof titanium was found at a level of negligence, about 0.02 μmol/cc. Incontrast, the resultant pale-yellow solid, which was obtained as thefinal supported catalyst, was determined by ICP to be 0.0433 mmlo/g. Asa result, a content of titanium removed by washing could be neglected.Therefore the content of titanium in a supported catalyst can becalculated directly from the content of titanium in an originalhomogeneous catalyst and the weight of the resultant supported catalyst.

[0076] The resultant pale-yellow solid was obtained as the finalsupported catalyst, and its titanium content was determined by ICP to be0.0433 mmlo/g. TABLE 1 SiO₂ SAN MAO HomoCat-1 Ti Content Example (g) (g)(mmol) (mmol) (mmol/g) 2 4 0.5 2.0 0.2 0.0433^(a)) 3 4 0.5 2.0 0.60.0433^(a)) 4 4 0.5 2.0 0.8 0.0433^(a)) 5 4 0.5 2.0 0.2 0.0433^(b)) 6 40.5 8.0 0.2 0.0433^(b)) 7 4 0.5 0.2 0.2 0.0433^(b)) 8 4 0.5 2.0 0.20.0433^(b)) 9 4 0.5 2.0 0.2 0.0433^(b)) 10 4 0.5 0 0.2 0.0433^(b)) 11 40.5 0 0.2 Cp * Ti(OCH₃)₃ Comp. Ex. 1 4 0 2.0 0.2 0.0433^(b))

[0077] a) Determination by ICP

[0078] b) Theoretical value by calculation

Examples 3-4

[0079] The same procedure as in Example 2 was followed with theexception that a homogeneous catalyst (HomoCat-1) was added as shown inTable 1.

Example 5

[0080] The same procedure as in Example 2 was followed with theexception that 0.2g of a SAN polymer was used for preparing a supportprecursor I, the content of components used are given in Table 1.

Examples 6-7

[0081] The same procedure as in Example 2 was followed with theexception that a MAO was added as shown in Table 1 for preparing asupport precursor II.

Example 8

[0082] To a dried 250 ml flask equipped with a magnetic stirrer, 4 g ofsilica, 2.0 mmol of methylaluminoxane in 80 ml of toluene were addedunder an atmosphere of nitrogen. The resultant slurry was stirred at aroom temperature for 30 minutes, and then the toluene was then removedby decantation followed by drying under vacuum. Thus, a white powder wasobtained.

[0083] SAN polymer (the same as Example 2) in 80 ml of toluene wasinjected by cannular to the white powder. The resultant slurry was keptat room temperature with stirring for 2 hours and then was filtered. Thesolid was washed with 50 ml of toluene for 3 times, and then was driedby vacuum As a result another white powder was obtained. 0.2 mmol ofHomoCat-1 prepared in Example 1, in 80 ml of toluene was injected to thewhite powder by cannular. The resultant slurry was stirred at a roomtemperature for 30 minutes, and then was filtered. The solid filteredwas washed with 50 ml of toluene for 3 times, and then was dried byvacuum. The resultant pale-yellow solid was obtained as the finalsupported catalyst, and its titanium content was determined by ICP to be0.0433 mmlo/g.

Example 9

[0084] The same procedure as in Example 2 was followed for preparing asupport precursor I. 0.2 mmol of HomoCat-1 prepared in Example 1 in 80ml of toluene was injected by cannular. The resultant slurry was stirredat a room temperature for 30 minutes, and then was filtered. The solidfiltered was treated with 2 mmol of MAO in 80 ml of toluene for another30 minutes at room temperature with stirring. The resultant slurry wasfiltered, and then washed with 50 ml of toluene for 3 times. Aftervacuum dry, a pale-yellow solid was obtained, and its titanium contentwas determined by ICP to be 0.0433 mmlo/g.

Example 10

[0085] The same procedure as in Example 2 was followed for preparing asupport precursor I. 0.2 mmol of HomoCat-1 prepared in Example 1 in 80ml of toluene was injected by cannular. The resultant slurry was stirredat a room temperature for 30 minutes, and then was filtered. The solidfiltered was washed with 50 ml of toluene for 3 times. After vacuum dry,a pale-yellow solid was obtained as the final supported catalyst, andits titanium content was determined by ICP to be 0.0433 mmol/g.

Example 11

[0086] The same procedure as in Example 5 was followed for preparing asupport precursor II. To this support catalyst II, 0.2 mmol of ahomogeneous catalyst, Cp*Ti(OCH₃)₃(Steam Chemicals Co. Ltd.) in 80 ml oftoluene was injected by cannular. The resultant slurry was stirred at aroom temperature for 30 minutes, and then was filtered. The solidfiltered was washed with 50 ml of toluene for 3 times. After vacuum dry,a pale-yellow solid was obtained as a supported catalyst, and itstitanium content was determined by ICP to be 0.0433 mmol/g.

Comparative Example 1

[0087] The same procedure as in Example 2 was followed with theexception that a SAN polymer was not used for preparing a supportprecursor I, the content of components used are given in Table 1.

Example 12

[0088] To a dried 1L glass reactor, equipped with a circulation waterjacket for temperature control and a double helical impeller (made ofsteel), 200 ml of a purified styrene monomer and 8 ml of 2 Mtriisobutylaluminum (TiBA) in toluene solution were added. The solutionwas stirred at 70° C. and 400 rpm for 10 minutes, and then 0.28 ml (0.8mmol) of 2.8 M of methylaluminoxane and 0.18 g (0.008 mmol) of asupported catalyst prepared in Example 2, which had been suspended in 3ml of toluene in advance, were injected successively until total amountof 0.04 mmol of a supported catalyst and 4 mmol of a methylaluminoxanewere injected. The total feeding time was 40 minutes and thepolymerization was processed another 80 minutes. The solution wasquenched by a large amount of methanol after total polymerization timeof 2 hours. The polymer was filtered and dried by vacuum at 150° C. As aresult, 84.9 g of a polymer was obtained. The conversion was 46.7% byweight and its activity was 44.4 kg/g Ti.

[0089] As a result of analysis of the polymer obtained by ¹³C NMR andDSC, the polymer was a highly syndiotactic polystyrene with the meltingpoint of 70° C. The weight average molecular weight (Mw) of the polymerdetermined by GPC was 540,400 and molecular weight distribution (Mw/Mn)was 2.22.

Examples 13-14

[0090] The same procedure as in Example 12 was followed with theexception that the supported catalysts, which have different contents oftitanium as shown in Table 1, prepared from Examples 3 and 4 were usedrespectively. The polymerization data were shown in Table 2.

Example 15

[0091] The same procedure as in Example 12 was followed with theexception that the supported catalyst prepared from Example 5 was used.The polymerization data were shown in Table 2.

Examples 16-17

[0092] The same procedure as in Example 12 was followed with theexception that the supported catalysts prepared from Examples 6 and 7were used respectively. The polymerization data were shown in Table 2.

Examples 18-19

[0093] The same procedure as in Example 12 was followed with theexception that the supported catalysts prepared from Examples 8 and 9were used respectively. The polymerization data were shown in Table 2.

Example 20

[0094] The same procedure as in Example 12 was followed with theexception that the supported catalyst prepared from Example 10 was used.The polymerization data were shown in Table 2.

Example 21

[0095] The same procedure as in Example 12 was followed with theexception that the supported catalyst prepared from Example 11 was used.The polymerization data were shown in Table 2. TABLE 2 ConversionActivity Supported Rate (kg/g Mw MWD Example Catalyst (%) Ti) (g/mol)(Mw/Mn) 12 Example 2 46.7 44.4 540,400 2.22 13 Example 3 43.8 41.6524,000 2.73 14 Example 4 51.3 48.8 560,800 4.44 15 Example 5 44.0 42.5559,400 2.35 16 Example 6 16.0 15.2 695,000 2.17 17 Example 7 43.0 40.1— — 18 Example 8 20.4 19.4 684,000 1.87 19 Example 9 17.5 16.6 557,0002.76 20 Example 10 26.4 25.5 — — 21 Example 11 28.4 27.4 — — ComparativeComparative 0 0 — — Example 2 Example 1

[0096] Polymerization conditions: 200 ml of styrene monomer, 0.04 mmolof total catalyst, 16 mmol of triisobutylaluminum (TiBA),[TiBA]/[Ti]=400, 4 mmol of total methylaluminoxane (MAO); 70° C. ofpolymerization temperature; 400 rpm; 2 hours of total polymerizationtime.

Comparative Example 2

[0097] The same procedure as in Example 12 was followed with theexception that the support precursor of the Comparative Example 1, whichwas prepared without using any SAN polymer, was used. No polymer wasobtained under the polymerization conditions listed in Table 2.

Example 22

[0098] In order to test a supported catalyst performance in a commercialscale, Example 22 was performed under enlarged scale.

[0099] A 1 L glass autoclave reactor was used as the supported catalystpolymerization reactor. To the completely dried reactor, 40 g of silica,5 g of styrene-acrylonitrile polymer were added under an atmosphere ofnitrogen. The reactor was evacuated at 70° C. for 30 minutes, 300 ml oftoluene was transferred to the reactor under pressurization of nitrogen.The reactor was kept at 70° C. with stirring at 400 rpm for 2 hours.After complete dissolution of the SAN polymer, toluene was removed bydecantation followed by drying under vacuum. 20 mmol ofmethylaluminoxane (MAO) in 200 ml of toluene was added. After stirringat 70° C. for 30 minutes, toluene was again removed by decantationfollowed by drying under vacuum, and then 2 mmol of a homogeneouscatalyst, HomoCat-1, prepared in Example 1 in 200 ml of toluene wasadded. After stirring at 70° C. for another 30 minutes, the slurry wasfiltered and the solid was washed with 100 ml of toluene for 3 times,and then was dried completely by vacuum. As a result, a pale-yellowpowder was obtained as the final product. Titanium content of theresultant pale-yellow solid was determined by ICP to be 0.0433 mmol/g.

Example 23

[0100] The same procedure as in Example 22 was followed with theexception of using 2 g of a SAN polymer instead of 5 g of a SAN polymer.

Example 24

[0101] The same procedure as in Example 22 was followed with theexception that the addition step of MAO was omitted.

[0102] To a completely dried reactor, 40 g of silica, 5 g ofstyrene-acrylonitrile polymer were added under an atmosphere ofnitrogen. The reactor was evacuated at 70° C. for 30 minutes, 300 ml oftoluene was transferred to the reactor under pressurization of nitrogen.The reactor was kept at 70° C. with stirring at 400 rpm for 2 hours.After complete dissolution of the SAN polymer, toluene was removed bydecantation followed by drying under vacuum. 2 mmol of a homogeneouscatalyst, HomoCat-1, prepared in Example 1 in 200 ml of toluene wasadded. After stirring at 70° C. for another 30 minutes, the slurry wasfiltered and the solid was washed with 100 ml of toluene for 3 times,and then was dried completely by vacuum. As a result, a pale-yellowpowder was obtained as the final product. Titanium content of theresultant pale-yellow solid was determined by ICP to be 0.0433 mmol/g.

Example 25

[0103] A 10 L autoclave reactor was purged with nitrogen at 100° C. for2 hours, and then was cooled to 70° C. 2000 ml of styrene monomer and 40ml of triisobutylaluminum (TiBA) in toluene solution were transferred tothe reactor by pressurization of nitrogen. The reactor was kept at 70°C. with stirring at 300 rpm for 10 minutes under an atmosphere ofnitrogen. 8 mmol of methylaluminoxane (MAO) and 0.08 mmol of supportedcatalyst (in toluene suspension) prepared in Example 22 were injected.The feeding operation of MAO and a supported catalyst, in the sameamount as mentioned above After stirring at 70° C. for 30 minutes,toluene was again removed by decantation followed by drying undervacuum, and then 2 mmol of a homogeneous catalyst, HomoCat-1, preparedin Example 1 in 200 ml of toluene was added. After stirring at 70° C.for another 30 minutes, the slurry was filtered and the solid was washedwith 100 ml of toluene for 3 times, and then was dried completely byvacuum. As a result, a pale-yellow powder was obtained as the finalproduct. Titanium content of the resultant pale-yellow solid wasdetermined by ICP to be 0.0433 mmol/g. TABLE 3 [Ti] Supported (mmol/[TiBA]/ Conversion Activity Example Catalyst L-SM) [Ti] (wt %) (kg/g Ti)25 Example 22 0.2 100 60.9 115.8 26 Example 22 0.1 150 29.9 113.7 27Example 22 0.1 200 28.4 108.0 28 Example 23 0.1 200 35.6 135.4 29Example 24 0.2 400 30.3  57.6

Examples 26-27

[0104] The same procedure as in Example 25 was followed with theexception that the concentration of a catalyst and the ratio of[TiBA]/[Ti] were different from those of Example 25. The results ofpolymerization reaction were shown in Table 3.

Example 28

[0105] The same procedure as in Example 25 was followed with theexception that the support precursor of the Example 23 was used. Theresults of polymerization reaction were shown in Table 3.

Example 29

[0106] The same procedure as in Example 25 was followed with theexception that the support precursor of the Example 24 was used. Theresults of polymerization reaction were shown in Table 3. TABLE 4 [Ti]Supported (mmol/ [TiBA]/ Activity Example Catalyst L-hexan) [Ti] Yield(kg/mol · Ti · hr) 30 2 0.2 100 0.09 2.2 Comp. 1 0.2 100 2.38 58 Ex. 3

Example 30

[0107] To a 1 L well-dried glass autoclave, 200 ml of polymerizationgrade hexane and 2 ml of 2 M triisobutylaluminum toluene solution wasintroduced under an atmosphere of nitrogen at 70° C. After stirring at700 rpm for 10 minutes, 0.92 g of a supported catalyst prepared inExample 2 was added as a suspension in 10 ml of toluene, and thenpolymerization grade ethylene was introduced. The reactor was kept at anethylene pressure of 60 psi for 1 hour. The polymerization reaction wasterminated with methanol and polymer was collected by filtration, thendried in vacuum. As a result, 2.3 g of polyethylene powder in sphericalmorphology was obtained. The activity of the catalyst was 58 kg/molTihr.

Comparative Example 3

[0108] The same procedure as in Example 30 was followed with theexception that the homogeneous precursor of the Example 1 was used. Theresults of polymerization reaction were shown in Table 4. TABLE 5 [Ti]Supported (mmol/ Activity Example Catalyst L-SM) [MAO]/[Ti] Yield(kg/mol · Ti · hr) 31 Example 2 0.1 500 6.92 346 Comp. Example 1 0.1 500— — Ex. 4

Example 31 Ethylene-Styrene Copolymerization

[0109] To a 1 L well-dried glass autoclave, 200 ml of purified styrenemonomer (SM) and 3.5 ml of 2.8 M methylaluminoxane toluene solution wasintroduced under an atmosphere of nitrogen at 70° C. After stirring at700 rpm for 10 minutes, 0.46 g (0.02 mmol) of a supported catalystprepared in Example 2 was added as a suspension in 10 ml of toluene, andthen polymerization grade ethylene was introduced. The reactor was keptat an ethylene pressure of 60 psi for 1 hour. The polymerizationreaction was terminated with methanol and polymer was collected byfiltration, and then dried in vacuum. As a result, 6.92 g of copolymerwas obtained. The activity of the catalyst was 346 kg/molTihr. Thepolymerization conditions and data were shown in Table 5.

Comparative Example 4

[0110] The same procedure as in Example 31 was followed with theexception that the homogeneous precursor of the Example 1 was used. Thepolymer obtained was analyzed by ¹³C NMR to be a syndiotacticpolystyrene, and no polyethylene or ethylene-containing copolymer wasfound.

[0111] The present invention has been described based on preferredembodiments of the present invention, but it should be apparent to thoseordinarily skilled in the art that various changes and modifications canbe added without departing from the spirit and scope of the presentinvention. Such changes modifications come within the scope of thepresent invention.

What is claimed is:
 1. A supported metallocene catalyst for polymerizinga syndiotactic styrenic polymer characterized in comprising (A) apolymer, (B) a support, and (C) a transition metal compound, the polymerfunctioning as an insulator to the support
 2. The supported metallocenecatalyst for polymerizing a syndiotactic styrenic polymer in claim 1,characterized in further comprising (D) (a) a compound which forms anionic complex by the reaction with the transition metal compound or (b)a specific oxygen-containing compound.
 3. The supported metallocenecatalyst for polymerizing a syndiotactic styrenic polymer in claim 2,characterized in further comprising (E) an alkylaluminum compound. 4.The supported metallocene catalyst for polymerizing a syndiotacticstyrenic polymer in claim 1, wherein said polymer (A) functions as aninsulator against the support (B).
 5. The supported metallocene catalystfor polymerizing a syndiotactic styrenic polymer in claim 1, whereinsaid polymer (A) is harmless to catalytic performances, chemical orphysical interaction with a catalyst and the surface of a support, andinsoluble in styrenic monomer or polymerization solvent after loading acatalyst.
 6. The supported metallocene catalyst for polymerizing asyndiotactic styrenic polymer in claim 1, wherein said polymer (A) is apolar group containing polymer selected from the group consisting ofacrylonitrile containing polymer and copolymer, hydroxyl groupcontaining polymer and copolymer, acrylic and acrylate polymer andcopolymer, maleic anhydride containing copolymer, acetate containingpolymer and copolymer, polyether, polyketone, and polyamide polymer andcopolymer.
 7. The supported metallocene catalyst for polymerizing asyndiotactic styrenic polymer in claim 6, wherein the polar groupcontaining polymer is a styrene-acrylonitrile (SAN) polymer.
 8. Thesupported metallocene catalyst for polymerizing a syndiotactic styrenicpolymer in claim 7, wherein said styrene-acrylonitrile (SAN) polymer hasa degree of polymerization of at least 5, and contains about 0.1 to 100%by weight of acrylonitrile.
 9. The supported metallocene catalyst forpolymerizing a syndiotactic styrenic polymer in claim 1, wherein thecontent of said polymer (A) is from about 0.001 to about 99.999 percentby weight.
 10. The supported metallocene catalyst for polymerizing asyndiotactic styrenic polymer of claim 1 in which said support is aninorganic material or an organic material.
 11. The supported metallocenecatalyst for polymerizing a syndiotactic styrenic polymer of claim 10 inwhich said inorganic material is selected from the group consisting ofsilica gel, alumina, silica-alumina gel, zeolite, mica powder, clays,molecular sieves, metal oxide compounds, metal halogenides, metalcarbonates and metal powder.
 12. The supported metallocene catalyst forpolymerizing a syndiotactic styrenic polymer of claim 1 in which saidorganic material is selected from the group consisting ofpoly(styrene-co-divinylbenzene) bead, starch powder and polyolefinpowder.
 13. The supported metallocene catalyst for polymerizing asyndiotactic styrenic polymer in claim 1, wherein the content of saidsupport (B) is from about 0.001 to about 99.999 percent by weight. 14.The supported metallocene catalyst for polymerizing a syndiotacticstyrenic polymer in claim 1, wherein said transition metal compound (C)is a metal compound of Group IVB of the Periodic Table.
 15. Thesupported metallocene catalyst for polymerizing a syndiotactic styrenicpolymer in claim 1, wherein the content of said transition metalcompound (C) is from about 0.0001 to about 30 percent by weight.
 16. Thesupported metallocene catalyst for polymerizing a syndiotactic styrenicpolymer in claim 1, wherein said component (a) comprising said component(D) is a borate compound, and wherein said component (b) is analkylaluminoxane.